CA2380408C - Coating compositions having improved scratch resistance, coated substrates and methods related thereto - Google Patents
Coating compositions having improved scratch resistance, coated substrates and methods related thereto Download PDFInfo
- Publication number
- CA2380408C CA2380408C CA002380408A CA2380408A CA2380408C CA 2380408 C CA2380408 C CA 2380408C CA 002380408 A CA002380408 A CA 002380408A CA 2380408 A CA2380408 A CA 2380408A CA 2380408 C CA2380408 C CA 2380408C
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- 239000008199 coating composition Substances 0.000 title claims abstract description 210
- 239000000758 substrate Substances 0.000 title claims description 250
- 238000000034 method Methods 0.000 title claims description 108
- -1 polysiloxane Polymers 0.000 claims abstract description 392
- 239000002245 particle Substances 0.000 claims abstract description 272
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 272
- 125000000524 functional group Chemical group 0.000 claims abstract description 217
- 239000000376 reactant Substances 0.000 claims abstract description 72
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims description 796
- 238000000576 coating method Methods 0.000 claims description 165
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 146
- 239000007787 solid Substances 0.000 claims description 143
- 239000011248 coating agent Substances 0.000 claims description 138
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 136
- 229920005862 polyol Polymers 0.000 claims description 123
- 239000000463 material Substances 0.000 claims description 115
- 238000012360 testing method Methods 0.000 claims description 98
- 230000000717 retained effect Effects 0.000 claims description 93
- 150000003077 polyols Chemical class 0.000 claims description 91
- 238000006243 chemical reaction Methods 0.000 claims description 86
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- 229920000642 polymer Polymers 0.000 claims description 70
- 239000003795 chemical substances by application Substances 0.000 claims description 68
- 239000008119 colloidal silica Substances 0.000 claims description 64
- 239000005056 polyisocyanate Substances 0.000 claims description 64
- 229920001228 polyisocyanate Polymers 0.000 claims description 64
- 239000002253 acid Substances 0.000 claims description 61
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 54
- 239000004094 surface-active agent Substances 0.000 claims description 53
- 239000010954 inorganic particle Substances 0.000 claims description 39
- 150000008064 anhydrides Chemical group 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 36
- 229920000058 polyacrylate Polymers 0.000 claims description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 33
- 230000005855 radiation Effects 0.000 claims description 32
- 238000010348 incorporation Methods 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
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- 230000036961 partial effect Effects 0.000 claims description 25
- 125000003700 epoxy group Chemical group 0.000 claims description 24
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 229920003180 amino resin Polymers 0.000 claims description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 125000003368 amide group Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 230000005865 ionizing radiation Effects 0.000 claims description 17
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011246 composite particle Substances 0.000 claims description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000004185 ester group Chemical group 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 12
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 10
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 9
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 8
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 claims description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 125000005275 alkylenearyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 4
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 3
- FHCIILYMWWRNIZ-UHFFFAOYSA-N benzhydryl(chloro)silane Chemical compound C=1C=CC=CC=1C([SiH2]Cl)C1=CC=CC=C1 FHCIILYMWWRNIZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- 229940073561 hexamethyldisiloxane Drugs 0.000 claims description 3
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical group OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 9
- 230000003678 scratch resistant effect Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 description 61
- 238000002360 preparation method Methods 0.000 description 58
- 238000001723 curing Methods 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
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- 239000000178 monomer Substances 0.000 description 46
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- 239000006185 dispersion Substances 0.000 description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 31
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 30
- 239000004593 Epoxy Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 229910052782 aluminium Inorganic materials 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 229920001451 polypropylene glycol Polymers 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
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- 239000007921 spray Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 22
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 17
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Applications Claiming Priority (7)
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| US36506999A | 1999-07-30 | 1999-07-30 | |
| US09/365,069 | 1999-07-30 | ||
| US17189899P | 1999-12-23 | 1999-12-23 | |
| US60/171,898 | 1999-12-23 | ||
| US48913200A | 2000-01-21 | 2000-01-21 | |
| US09/489,132 | 2000-01-21 | ||
| PCT/US2000/020838 WO2001009259A1 (en) | 1999-07-30 | 2000-07-31 | Coating compositions having improved scratch resistance, coated substrates and methods related thereto |
Publications (2)
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| CA2380408A1 CA2380408A1 (en) | 2001-02-08 |
| CA2380408C true CA2380408C (en) | 2008-04-22 |
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| CA002380408A Expired - Fee Related CA2380408C (en) | 1999-07-30 | 2000-07-31 | Coating compositions having improved scratch resistance, coated substrates and methods related thereto |
Country Status (10)
| Country | Link |
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| US (3) | US6593417B1 (pt) |
| EP (1) | EP1204708A1 (pt) |
| JP (3) | JP2003506518A (pt) |
| KR (1) | KR100760068B1 (pt) |
| CN (1) | CN1209427C (pt) |
| AU (1) | AU771279B2 (pt) |
| BR (1) | BR0012875A (pt) |
| CA (1) | CA2380408C (pt) |
| MX (2) | MX270896B (pt) |
| WO (1) | WO2001009259A1 (pt) |
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-
2000
- 2000-07-31 CN CNB008133476A patent/CN1209427C/zh not_active Expired - Fee Related
- 2000-07-31 AU AU63929/00A patent/AU771279B2/en not_active Ceased
- 2000-07-31 CA CA002380408A patent/CA2380408C/en not_active Expired - Fee Related
- 2000-07-31 JP JP2001514054A patent/JP2003506518A/ja not_active Withdrawn
- 2000-07-31 MX MXPA02001097 patent/MX270896B/es active IP Right Grant
- 2000-07-31 MX MXPA00201018 patent/MX253908B/es unknown
- 2000-07-31 BR BR0012875-9A patent/BR0012875A/pt not_active Application Discontinuation
- 2000-07-31 US US09/629,443 patent/US6593417B1/en not_active Expired - Fee Related
- 2000-07-31 KR KR20027001351A patent/KR100760068B1/ko not_active Expired - Lifetime
- 2000-07-31 EP EP00950899A patent/EP1204708A1/en not_active Withdrawn
- 2000-07-31 WO PCT/US2000/020838 patent/WO2001009259A1/en not_active Ceased
-
2003
- 2003-06-09 US US10/456,552 patent/US6759478B2/en not_active Expired - Lifetime
-
2004
- 2004-02-24 US US10/784,830 patent/US7005472B2/en not_active Expired - Lifetime
-
2005
- 2005-08-23 JP JP2005241909A patent/JP2006057098A/ja not_active Withdrawn
-
2009
- 2009-04-22 JP JP2009104573A patent/JP2009197238A/ja not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US6759478B2 (en) | 2004-07-06 |
| WO2001009259A1 (en) | 2001-02-08 |
| AU6392900A (en) | 2001-02-19 |
| CA2380408A1 (en) | 2001-02-08 |
| CN1209427C (zh) | 2005-07-06 |
| AU771279B2 (en) | 2004-03-18 |
| MX253908B (es) | 2008-01-28 |
| MXPA02001097A (es) | 2003-07-21 |
| KR20020056882A (ko) | 2002-07-10 |
| CN1376187A (zh) | 2002-10-23 |
| JP2003506518A (ja) | 2003-02-18 |
| KR100760068B1 (ko) | 2007-09-18 |
| JP2006057098A (ja) | 2006-03-02 |
| US20040225057A1 (en) | 2004-11-11 |
| WO2001009259A9 (en) | 2002-07-18 |
| US20030212199A1 (en) | 2003-11-13 |
| BR0012875A (pt) | 2002-04-16 |
| US7005472B2 (en) | 2006-02-28 |
| MX270896B (es) | 2009-10-14 |
| US6593417B1 (en) | 2003-07-15 |
| EP1204708A1 (en) | 2002-05-15 |
| JP2009197238A (ja) | 2009-09-03 |
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